Manufacture of dyestuffs of the anthraquinone series



Patented Dec. 3, 1935 UNITED STATES MANUFACTURE OF DYESTUFFS OF THEANTHRAQUINONE SERIES Henry Dreyfus, London, England No Drawing. Originalapplication January 22,

1927, Serial No. 162,936. Divided and this application September 19,1931, Serial No. 563,907. In Great Britain November 23, 1926 12 Claims.

This invention relates to the manufacture of dyestuffs of theanthraquinone series and is more particularly directed to themanufacture of hydroxy alkylamino anthraquinones.

According to the present invention hydroxy alkylamino anthraquinones areprepared by acting upon an anthraquinone containing a phenolic orhalogen group or groups, 1. e. negatively substituted anthraquinones,with an amino alcohol. In the case of treating anthraquinones containinga phenolic group or groups it is extremely advantageous to reduce thecompound to the leuco state in order to bring it to reaction with theamino alcohol. Furthermore a substituted products are best treatedaccording to the present invention, and in the case of an a-hydroxyanthraquinone it is advantageous to use as starting material a l-hydroxyanthraquinone containing an amino or hydroxy group in the 4-position.

As examples of amino alcohols which may be employed according to thepresent invention I may instance B-amino ethyl alcohol (monoethanolamine) and -amino-u {3 dihydroxy propane.

The dyestuffs prepared according to the present invention are veryvaluable for the coloration, e. g. dyeing, printing or stencilling, ofmaterials made of or containing cellulose acetate or other organicesters of cellulose, such for example as cellulose formate, propionateor butyrate, or the product obtained by the treatment of alkalizedcellulose with paratoluene sulpho-chloride (e. g. the product known asimmunized cotton), or made of or containing cellulose ethers, such asmethyl, ethyl or benzyl cellulose. The application of the dyestuffs tothese materials forms the subject matter of my co-pending application S.No. 162,936 filed January 22, 1927, patented April 19, 1932, Patent No.1,854,460, from which the present application is a divisionalapplication.

The following examples illustrate the manufacture of the dyestuffsaccording to the present invention:---

Example 1 a-chloranthraquinone is heated in an autoclave with excess offl-amino-ethyl alcohol and methylated spirits until reaction iscomplete. The

mass is allowed to cool, filtered and purified. The

product IIIEE-GHr-CHaOH 0 dyes cellulose acetate a full shade ofscarlet.

Example 2 1-hydroxy-4-aminoanthraquinone is reduced to the leuco stateby treatment with caustic soda and sodium hydrosulphite and the leucobody precipitated by pouring into hydrochloric acid. The driedprecipitate is refluxed on a. water bath with slightly more than 1molecular proportion of paminoethyl alcohol and methylated spirits. Theresulting leuco compound is oxidized to yield a dyestufi of the probableformula C) I IHn The dyestuff dyes cellulose acetate a bluish violetshade.

In a similar manner other oxy alkylamino anthraquinones may be producedas for example:

1,4-di(B-hydroxy-ethylamino) -anthra.quinone, which dyes celluloseacetate a pure blue shade,

1-hydroxy-4 B hydroxy ethylamino anthraquinone which dyes celluloseacetate violet.

What I claim and desire to secure by Letters Patent is:-

1. Process for the manufacture of anthraquinone dyestuffs whichcomprises reacting with an amino alcohol on an a-negatively-substitutedanthraquinone in which the negative substituent is capable of beingreplaced by an amino group by the action of an amine.

2. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting an oc-ChlOl anthraquinone with an amino alcohol.

3. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting an a-ChlOl anthraquinone with B-amino-ethyl alcohol.

4. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting a leuco a-hydroxy anthraquinone with an amino alcohol.

5. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting with an amino alcohol upon a leuco anthraquinone containing atleast one hydroxy group in an a-position and at least one amino group inan u-position.

6. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting with an amino alcohol upon a leuco anthraquinone containing atleast one hydroxy group in the u-position.

'7. Process for the manufacture of anthraquinone dyestufis, comprisingreacting a leuco a-hydroxy anthraquinone with fi-amino-ethyl alcohol.

8. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting with p-aminoethyl alcohol upon a leuco anthraquinone containingat least one hydroxy group in an a-position and at least one amino groupin an a-position.

9. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting with p-aminoethyl alcohol upon a leuco anthraquinone containingat least one hydroxy group in the a-position.

10. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting with an amino alcohol upon a leuco anthraquinone containing ahydroxy group in the 1-position and a hydroxy group in the 4-position.

11. Process for the manufacture of anthraquinone dyestuffs, comprisingreacting with an amino alcohol upon a leuco anthraquinone containing ahydroxy group in the 1-position and an amino group in the 4-position.

12. Process for the manufacture of anthraquinone dyestuifs, comprisingreacting with p-amino ethyl alcohol upon a leuco anthraquinonecontaining a hydroxy group in the 1-position and a hydr-oxy group in the4-position.

v HENRY DREYFUS.

